Journal
BIOCHEMISTRY
Volume 40, Issue 34, Pages 10023-10031Publisher
AMER CHEMICAL SOC
DOI: 10.1021/bi010391+
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Here we demonstrate that monovalent cations can localize around B-DNA in geometrically regular, sequence-specific sites in oligonucleotide crystals. Positions of monovalent ions were determined from high-resolution X-ray diffraction of DNA crystals grown in the presence of thallium(1) cations (T1(+)). T1(+) has previously been shown to be a useful K+ mimic. T1(+) positions determined by refinement of model to data are consistent with positions determined using isomorphous F-Tl - F-K difference Fouriers and anomalous difference Fouriers. None of the observed T1(+) sites surrounding CGCGAATTCGCG are fully occupied by Tl+ ions. The most highly occupied sites, located within the G-tract major groove, have estimated occupancies ranging from 20% to 35%. The occupancies of the minor groove sites are estimated to be around 10%. The T1(+) positions in general are not in direct proximity to phosphate groups. The A-tract major groove appears devoid of localized cations. The majority of the observed T1(+) ngaged in lattice interactions or crystal packing. The locations of the cation sites are dictated by coordination geometry, electronegative potential, avoidance of electropositive amino groups, and cation-pi interactions. It appears that partially dehydrated monovalent cations, hydrated divalent cations, and polyamines compete for a common binding region on the floor of the G-tract major groove.
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